CN102792493A - Nonaqueous secondary cell - Google Patents
Nonaqueous secondary cell Download PDFInfo
- Publication number
- CN102792493A CN102792493A CN2011800127079A CN201180012707A CN102792493A CN 102792493 A CN102792493 A CN 102792493A CN 2011800127079 A CN2011800127079 A CN 2011800127079A CN 201180012707 A CN201180012707 A CN 201180012707A CN 102792493 A CN102792493 A CN 102792493A
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- CN
- China
- Prior art keywords
- carbon
- secondary batteries
- aqueous secondary
- sio
- porous layer
- Prior art date
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- 150000004862 dioxolanes Chemical class 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002732 mesitylenes Chemical class 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Abstract
The disclosed nonaqueous secondary cell contains a positive electrode, a negative electrode, a nonaqueous electrolyte and a separator. The negative electrode contains a composite body comprising a covering layer of carbon formed on the surface of a core member containing Si and O as constituent elements, and a negative electrode active substance containing a graphitic carbon material, wherein the carbon content of the composite body is 10-30 mass%. When the Raman spectrum of the composite body is measured with a 532 nm-wavelength laser, the intensity ratio I510/I1343 (the ratio of the peak intensity I510 at 510 cm-1 originating from Si to the peak intensity I1343 at 1343cm-1 originating from carbon) is 0.25 or less, and when measuring the size of Si-phase crystallites contained in the core material by the X-ray diffraction method using CuK[alpha] radiation, the half value width of the Si (111) diffraction peak is less than 3.0 degrees.
Description
Technical field
The present invention relates to have the non-aqueous secondary batteries of excellent storage characteristic.
Background technology
The non-aqueous secondary batteries that with the lithium rechargeable battery is representative is high voltage, high power capacity, and therefore the power supply as various portable equipments is extensively adopted.The purposes that demonstrates in recent years in addition in medium-sized, large-scale specifications such as electric power tools such as electric tool (power tool), electric automobile, electrodynamic type bicycle also enlarges.
Particularly, in employed batteries such as the portable phone of miniaturization and multifunction progress, game machine, require further high capacity,, show research, the development progress of the electrode active material of high charge-discharge capacity as its method.Wherein, as the active material of negative pole, replace the material with carbon elements such as graphite that adopt in the non-aqueous secondary batteries in the past, the material that silicon (Si), tin (Sn) etc. can occlusions, emit more lithiums (ion) receives publicity.Particularly, reported to have at SiO
2In be dispersed with the SiO of the ultramicronized structure of Si
xAlso have both characteristics (with reference to patent documentation 1,2) such as part throttle characteristics excellence.
Yet, also known above-mentioned SiO
xCan produce following problems: with the expansion that discharges and recharges the volume that reacting phase follows, shrink big; Therefore each charge and discharge cycles of battery all can sized particles; Si that separate out on the surface and nonaqueous electrolytic solution react and the increase of irreversible capacity, and perhaps battery is heaved owing to discharge and recharge, or the like.In addition, SiO
xHas fine shape, though thus the improvement of the part throttle characteristics of battery has been confirmed certain effect, SiO
xThis still leaves room for improvement in this as the low material of conductivity.
In view of such situation, restriction SiO has been proposed also
xUtilance suppress and discharge and recharge the SiO that reacting phase is followed
xExpansion, the contraction of volume, or with SiO
xThe surface be covered with conductive materials such as carbon and improve part throttle characteristics; Or (for example added through the substituted cyclic carbonate of halogen through use; 4-fluoro-1,3-dioxolanes-2-ketone etc.), the nonaqueous electrolytic solution of vinylene carbonate etc. improves the technology (with reference to patent documentation 3) of the charge of battery.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-47404 communique
Patent documentation 2: TOHKEMY 2005-259697 communique
Patent documentation 3: TOHKEMY 2008-210618 communique
Summary of the invention
Invent problem to be solved
Yet, with SiO
xThe non-aqueous secondary batteries that is used for negative pole can not satisfy the desired various characteristics of battery, and particularly, the improvement of storage characteristics becomes main problem.
The present invention proposes in view of said circumstances, provides high power capacity and storage characteristics excellent non-aqueous secondary batteries.
Be used to solve the method for problem
Non-aqueous secondary batteries of the present invention; It is characterized in that, be the non-aqueous secondary batteries with positive pole, negative pole, nonaqueous electrolyte and dividing plate, and above-mentioned negative pole contains negative electrode active material; Said negative electrode active material comprises: in constituting element, contain complex and graphite matter material with carbon element that the coating of surface formation carbon of the core of Si and O forms; Carbon content in the above-mentioned complex is 10～30 quality %, when measuring the Raman spectrum of above-mentioned complex with optical maser wavelength 532nm, derives from the 510cm of Si
-1Peak intensity I
510With the 1343cm that derives from carbon
-1Peak intensity I
1343Strength ratio I
510/ I
1343Be below 0.25, when having used the Alpha-ray X-ray diffraction method of CuK to measure the crystallite size of the Si phase that above-mentioned core comprised, the half width of (111) diffraction maximum of Si is less than 3.0 °.
The effect of invention
According to the present invention, can provide high power capacity and storage characteristics excellent non-aqueous secondary batteries.
Description of drawings
Figure 1A is the plane graph of non-aqueous secondary batteries of the present invention, and Figure 1B is the sectional view of non-aqueous secondary batteries of the present invention.
Fig. 2 is the stereogram of the outward appearance of demonstration non-aqueous secondary batteries of the present invention.
Embodiment
Non-aqueous secondary batteries of the present invention has negative pole, positive pole, nonaqueous electrolyte and dividing plate, and about formation except negative pole and structure, not special restriction can be used known all the time various formations and structure that non-aqueous secondary batteries adopted.Below, each inscape of non-aqueous secondary batteries of the present invention is detailed.
(negative pole)
The related negative pole of non-aqueous secondary batteries of the present invention can use the negative pole that for example has the structure of the anode mixture layer that comprises negative electrode active material, adhesive and conductive auxiliary agent as required etc. at the one or both sides of collector body.
The negative electrode active material that uses in the negative pole of non-aqueous secondary batteries of the present invention comprises: in constituting element, contain complex and graphite matter material with carbon element that the coating of surface formation carbon of the core of Si and O forms.
Above-mentioned core except the oxide of Si, can be the composite oxides of Si and other metal, can comprise the micro-crystallization or the amorphous phase of Si, other metal in addition.Preferred especially the use has at amorphous SiO
2Be dispersed with the material of the structure of small Si phase in the matrix.In this case, above-mentioned core is to form general formula SiO
x(wherein, x is 0.5≤x≤1.5.) expression.For example, have at amorphous SiO
2Be dispersed with structure and the SiO of Si in the matrix
2With the mol ratio of Si be under the situation of compound of 1:1, as composition formula, represent with SiO.
Below, to the SiO that forms as the representativeness of above-mentioned core
xDetail.
SiO
xLack electrical conductivity,, need conductive auxiliary agents such as material with carbon element therefore for it is used as negative electrode active material.Among the present invention, as stated, through using at SiO
xThe surface form the complex that the coating of carbon forms (below, be called SiO
x/ carbon complex.) as negative electrode active material, and only use SiO
xMix with conductive auxiliary agent such as material with carbon element and the situation of material compare, the conductive network in the anode mixture layer that comprises negative electrode active material is formed well, the part throttle characteristics of battery is improved.
In addition, among the present invention, through with (1) at the amount of the carbon of the surface sediment of core and state, (2) SiO
xIn the crystallite size optimization of Si phase, can keep the such characteristic of high power capacity, improve storage characteristics simultaneously.Below, specify.
As the SiO that becomes core
x, except SiO
xPrimary particle beyond, can enumerate the SiO that comprises a plurality of particles
xCompound particle, be the SiO of purpose with the conductivity that improves core etc.
xGranulation body that forms with the material with carbon element granulation etc.If the surface of such core is covered with material with carbon element, then as stated, the effects such as part throttle characteristics of the battery that can be improved, particularly, with SiO
xUnder the situation about being covered with material with carbon element with the surface of the granulation body of material with carbon element, can expect effect further.
At SiO as core
xIf the amount of carbon of surface sediment very few, the capacity after then storing reduces big, if too much, then can not bring into play the SiO of high power capacity fully
xAdvantage, therefore preferably with respect to SiO
xThe total amount of/carbon complex is 10～30 quality %.
Under the situation about exposing on the surface of core, store the back capacity and be easy to reduce, so the ratio that core is covered is high more good more, measure SiO to measure optical maser wavelength 532nm
xDuring the Raman spectrum of/carbon complex, derive from the 510cm of Si
-1Peak intensity: I
510With the 1343cm that derives from carbon (C)
-1Peak intensity: I
1343Strength ratio: I
510/ I
1343Be preferably below 0.25.Strength ratio: I
510/ I
1343More little, mean that then carbon lining rate is high more.
The strength ratio I of above-mentioned Raman spectrum
510/ I
1343Obtain as follows: with micro-raman spectroscopy method to SiO
x/ carbon complex is carried out to picture and measures (measurement range: 80 * 80 μ m, 2 μ m step-lengths), the whole spectrum in the measurement range is averaged, by Si peak (510cm
-1) and C peak (1343cm
-1) volume efficiency obtain.
In addition; If the crystallite size of the Si phase that core comprised is too small; Capacity after then storing reduces big, and therefore as long as the half width of (111) diffraction maximum through having used the Si that the Alpha-ray X-ray diffraction method of CuK obtains is preferably below 2.5 ° less than 3.0 °.On the other hand, if the crystallite size of Si phase is excessive, then the charge/discharge capacity at initial stage reduces, so half width is preferably more than 0.5 °.
SiO in the negative electrode active material
xThe content of/carbon complex is more than the 0.01 quality % below the 20 quality % in the whole desired of negative electrode active material.Through making above-mentioned content is more than the 0.01 quality %, can guarantee well by using SiO
xThe effect of the high capacity that brings in addition, is below the 20 quality % through making above-mentioned content, can avoid the SiO that accompanies with the whole repeated charge of negative electrode active material more well
xThe caused problem of change in volume, suppress capacity deterioration.
In addition, SiO
xThe average grain diameter of/carbon complex is preferably 0.5～20 μ m.If above-mentioned average grain diameter is below the 0.5 μ m, then the capacity deterioration after the repeated charge if be more than the 20 μ m, is then increased by the expansion that discharges and recharges the negative pole that causes.In addition, so-called average grain diameter makes these microparticulate in not having the medium of dissolving resin and measure the average grain diameter D of the volume reference that obtains for for example using laser light scattering particle size distribution meter (for example, hole field make made " LA-920 ") in this specification
50
As lining SiO
xThe material with carbon element on surface, for example can enumerate low-crystalline carbon, CNT, gas-phase growth of carbon fibre etc.
As the details of above-mentioned material with carbon element, be preferably at least a kind of material that is selected from the group of forming by material with carbon element, carbon black (comprising acetylene black, Ketjen black), Delanium, easy graphitized carbon and the difficult graphitized carbon of fibrous or spiral (coil) shape.Be easy to form conductive network and surface area big aspect, be preferably fibrous or spiral helicine material with carbon element.Have high conductivity, the high fluidity of protecting, in addition, even have SiO
xParticle expand to shrink and also to be easy to keep the properties that contact with this particle, preferred carbon black (comprising acetylene black, Ketjen black), easy graphitized carbon and difficult graphitized carbon.
In addition, for above-mentioned material with carbon element,, also can use graphite matter material with carbon element with SiOx and usefulness as negative electrode active material.Graphite matter material with carbon element also likewise has high conductivity, the high fluidity of protecting with carbon black etc., in addition, even have SiO
xParticle expand to shrink and also to be easy to keep the character that contact with this particle, therefore can be preferred for formation and SiO
xComplex.
In above-mentioned illustrative material with carbon element, as with SiO
xComplex be the material with carbon element that uses under the situation of granulation body, be preferably fibrous material with carbon element especially.This be because, fibrous material with carbon element be shaped as the filament shape, flexibility is high, therefore can follow the SiO that accompanies with discharging and recharging of battery
xExpansion shrink, in addition, bulk density is big, therefore can with SiO
xParticle has a large amount of junction points.As fibrous carbon, for example can enumerate, polyacrylonitrile (PAN) based carbon fiber, pitch-based carbon fiber, gas-phase growth of carbon fibre, CNT etc. can use they any.
In addition, fibrous material with carbon element can also for example be formed on SiO through vapor growth method
xThe surface of particle.
SiO
xResistivity value be generally 10
3～10
7K Ω cm, relative therewith, the resistivity value of above-mentioned illustrative material with carbon element is generally 10
-5～10k Ω cm.
In addition, SiO
x/ carbon complex can further have the material layer (material layer that comprises difficult graphitized carbon) of the coating of the carbon that covers particle surface.
The SiO that uses in the negative pole of the present invention
xIn/the carbon complex, about SiO
xWith the ratio of material with carbon element, from bringing into play viewpoint well, with respect to SiO by the effect that produces with compoundization of material with carbon element
x: 100 mass parts, material with carbon element are preferably more than 5 mass parts, more preferably more than 10 mass parts.In addition, in the above-mentioned complex, and if SiO
xThe ratio of the material with carbon element of compoundization is too much, then might cause the SiO in the anode mixture layer
xThe reduction of amount, the effect of high capacity reduces, therefore with respect to SiO
x: 100 mass parts, material with carbon element are preferably below 50 mass parts, more preferably below 40 mass parts.
Above-mentioned SiO
x/ carbon complex can obtain through for example following method.
At first, to becoming the SiO of core
xManufacture method describe.SiO
xThrough with Si and SiO
2Mixture heating, method such as the gas cooled of the silica that is generated separated out obtains.In addition, through SiO with gained
xUnder non-active gas atmosphere, heat-treat, can be in the small Si phase of the inner formation of particle.Through adjustment heat treatment temperature and the time of this moment, can control the half width of (111) diffraction maximum of formed Si phase.Usually, as long as heat treatment temperature is made as about 900～1400 ℃ scope, heat treatment time is got final product in about 0.1～10 hour scope setting.
As SiO
x, as stated, except SiO
xPrimary particle beyond, can enumerate SiO
xCompound particle, SiO
xWith the granulation body of material with carbon element, below, also with they unified " SiO that is called
xParticle ".
SiO
xCompound particle is for example through preparing in decentralized medium, to be dispersed with SiO
xDispersion liquid, it is carried out spray drying obtains.As decentralized medium, for example can use ethanol etc.The spraying of dispersion liquid is suitable in 50～300 ℃ atmosphere usually.
SiO
xUsed the mechanical means of oscillating mode, planet-shaped ball mill, rod mill etc. with the granulation body of material with carbon element through employing, made SiO
xObtain with the material with carbon element granulation.
Next, to above-mentioned SiO
xThe manufacture method of/carbon complex describes.For example, through with SiO
xParticle (SiO
xCompound particle or SiO
xGranulation body with material with carbon element) and hydrocarbon system gas in gas phase, heat, make the coke build-up that generates by the thermal decomposition of hydrocarbon system gas at SiO
xOn the surface of particle, thereby make SiO
x/ carbon complex.Like this, according to vapor phase growth (CVD) method, hydrocarbon system gas spreads over compound particle everywhere; In the hole on the surface of particle, surface, can form and comprise the thin of material with carbon element with conductivity and epithelium uniformly; That is, the coating of carbon therefore can be to SiO by a spot of material with carbon element
xParticle is given conductivity equably.
About the treatment temperature (atmosphere temperature) of vapor phase growth (CVD) method, according to the difference of the kind of hydrocarbon system gas and difference, it is suitable being generally 600～1200 ℃, wherein, is preferably more than 700 ℃, further is preferably more than 800 ℃.This is because can form the less remaining of impurity when treatment temperature is high and comprise the coating of the high carbon of conductivity.
As the liquid source of hydrocarbon system gas, can use toluene, benzene, xylenes, 1,3,5-trimethylbenzenes etc. are preferably especially and handle easy toluene.Through making their gasifications (for example, carrying out bubbling), can obtain hydrocarbon system gas with nitrogen.In addition, also can use methane gas, acetylene gas etc.
In addition, can through vapor phase growth (CVD) method with SiO
xParticle (SiO
xCompound particle or SiO
xGranulation body with material with carbon element) after surface is covered with material with carbon element; Make that to be selected from by oil be after at least a kind of organic compound in the group formed of the condensation product of pitch, thermosetting resin and naphthalene sulfonate and the aldehydes of pitch, coal measures is attached to the coating that comprises material with carbon element, the particle that is attached with above-mentioned organic compound to be burnt till.
Particularly, prepare in decentralized medium, to be dispersed with the surface by the SiO of material with carbon element lining
xParticle (SiO
xCompound particle or SiO
xGranulation body with material with carbon element) and the dispersion liquid of above-mentioned organic compound, this dispersion liquid is carried out spray drying, form, the particle that has been covered by this organic compound is burnt till by the particle of organic compound lining.
As above-mentioned pitch, can use isotropic pitch.In addition, as above-mentioned thermosetting resin, can use phenol resin, furane resins, furfural resin etc.As the condensation product of naphthalene sulfonate and aldehydes, can use naphthalene sulfonic acid-formaldehyde condensation product.
Make the surface by the SiO of material with carbon element lining as being used to
xParticle (SiO
xCompound particle or SiO
xGranulation body with material with carbon element) and the decentralized medium that disperses of above-mentioned organic compound, for example can use water, alcohols (ethanol etc.).The spraying of dispersion liquid is suitable in 50～300 ℃ atmosphere usually.It is suitable that firing temperature is generally 600～1200 ℃, wherein is preferably more than 700 ℃, further is preferably more than 800 ℃.This is because can form the less remaining of impurity when treatment temperature is high and comprise the coating of the high better quality material with carbon element of conductivity.Yet requiring treatment temperature is SiO
xFusing point below.
As negative electrode active material and and SiO
xAnd the graphite material of usefulness, the employed graphite material of lithium rechargeable battery that suitable use is known all the time for example can use native graphites such as flaky graphite; With easy graphitized carbons such as pyrolytic carbon class, mesophase-carbon micro-beads (MCMB), carbon fibers at Delanium that has carried out graphitization processing more than 2800 ℃ etc.
The adhesive that uses in the anode mixture layer, suitable use for example gather vinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) etc.In addition, in the anode mixture layer,, can add various carbon blacks, CNT, carbon fibers etc. such as acetylene black as conductive auxiliary agent.
In the anode mixture layer, can also add conductive material as conductive auxiliary agent.As such conductive material; As long as in non-aqueous secondary batteries, do not cause chemical change; Not special the qualification; For example can use carbon black (thermal black, furnace black, channel black, Ketjen black, acetylene black etc.), carbon fiber, metal powder (powder of copper, nickel, aluminium, silver etc.), metallic fiber, polyphenylene derivative more than 1 kinds or 2 kinds of material such as (materials that japanese kokai publication sho 59-20971 communique is put down in writing).Wherein, preferably use carbon black, more preferably Ketjen black, acetylene black.
The particle diameter of the material with carbon element that uses as conductive auxiliary agent for example is preferably more than the 0.01 μ m in average grain diameter, more preferably more than the 0.02 μ m, in addition, is preferably below the 10 μ m, more preferably below the 5 μ m.
Negative pole involved in the present invention for example can be made via following operation; Said operation is: modulation make negative electrode active material and adhesive, further as required conductive auxiliary agent be dispersed in the pasty state that forms in N-N-methyl-2-2-pyrrolidone N-(NMP), the water equal solvent or pulpous state the composition that contains cathode agent (wherein; Adhesive can be dissolved in the solvent); It is coated on the one or both sides of collector body, after the drying, implements compression process as required.Yet the manufacturing approach of negative pole of the present invention is not limited to said method, can adopt other manufacturing approach to make.
Each face that the thickness of anode mixture layer is preferably at collector body is 10～100 μ m.The density of anode mixture layer is calculated by the quality and the thickness of the anode mixture layer of the per unit area that is stacked on collector body, is preferably 1.0～1.9g/cm
3In addition, as the composition of anode mixture layer, for example, the amount of negative electrode active material is preferably 80～99 quality %, and the amount of adhesive is preferably 1～20 quality %, and under the situation of using conductive auxiliary agent, its amount is preferably 1～10 quality %.
As the collector body of negative pole, can use paper tinsel, stamped metal, net, expansion alloy of copper, nickel system etc., but use Copper Foil usually.For this negative electrode collector, under the situation that makes the whole thin thickness of negative pole for the battery that obtains high-energy-density, the upper limit of thickness is preferably 30 μ m, in order to ensure mechanical strength, and the following 5 μ m that are limited to of expectation thickness.
(positive pole)
The positive pole that non-aqueous secondary batteries of the present invention is related for example can use, and has the positive pole of the structure of the anode mixture layer that comprises positive active material, adhesive and conductive auxiliary agent etc. at the one or both sides of collector body.
The positive active material that uses in the positive pole as non-aqueous secondary batteries of the present invention can use and can occlusion emit transition metal oxide that contains Li of Li (lithium) ion etc.As the transition metal oxide that contains Li, can enumerate the transition metal oxide that contains Li that uses in the known all the time non-aqueous secondary batteries such as lithium rechargeable battery, particularly, can enumerate Li
yCoO
2(wherein, 0≤y≤1.1.), Li
zNiO
2(wherein, 0≤z≤1.1.), Li
eMnO
2(wherein, 0≤e≤1.1.), Li
aCo
bM
1 1-bO
2(wherein, above-mentioned M
1Be selected from least a kind of metallic element in the group of forming by Mg, Mn, Fe, Ni, Cu, Zn, Al, Ti, Ge and Cr, 0≤a≤1.1,0＜b＜1.0.), Li
cNi
1-dM
2 dO
2(wherein, above-mentioned M
2Be selected from least a kind of metallic element in the group of forming by Mg, Mn, Fe, Co, Cu, Zn, Al, Ti, Ge and Cr, 0≤c≤1.1,0＜d＜1.0.), Li
fMn
gNi
hCo
1-g-hO
2(wherein, 0≤f≤1.1,0＜g＜1.0,0＜h＜1.0.) wait the transition metal oxide that contains Li with layer structure etc., can only use wherein a kind, also can and with more than 2 kinds.
The adhesive that uses in the anode mixture layer can use illustrative various adhesives identical adhesive previous with the adhesive of using as anode mixture layer.
As the conductive auxiliary agent that uses in the anode mixture layer, for example can enumerate graphite (graphite matter material with carbon element) such as native graphite (flaky graphite etc.), Delanium; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, dim, thermal black; Carbon fiber; Deng material with carbon element etc.
Positive pole involved in the present invention is for example made via following operation; Said operation is: the pasty state that modulation is dispersed in positive active material, adhesive and conductive auxiliary agent to form in the NMP equal solvent or the composition that contains anode mixture of pulpous state are (wherein; Adhesive can be dissolved in the solvent); It is coated on the one or both sides of collector body, after the drying, implements compression process as required.Yet anodal manufacturing approach is not limited to said method, can adopt other manufacturing approach to make.
Each face that the thickness of anode mixture layer for example is preferably at collector body is 10～100 μ m.The density of anode mixture layer is calculated by the quality and the thickness of the anode mixture layer of the per unit area that is stacked on collector body, is preferably 3.0～4.5g/cm
3In addition, as the composition of anode mixture layer, for example, the amount of positive active material is preferably 60～95 quality %, and the amount of adhesive is preferably 1～15 quality %, and the amount of conductive auxiliary agent is preferably 3～20 quality %.
Anodal collector body can use the same collector body of collector body that uses in the positive pole with known non-aqueous secondary batteries all the time, and for example, preferred thickness is the aluminium foil of 10～30 μ m.
Among the present invention, when the quality with above-mentioned positive active material be made as P, when the quality of above-mentioned negative electrode active material is made as N, expectation P/N is 1.0～3.6.Through the higher limit that makes the P/N ratio is below 3.6, can reduce the utilance of negative electrode active material and limits charging capacitor, the SiO in the time of therefore can suppressing above-mentioned discharging and recharging
xThe expansion of the volume of/carbon complex, contraction prevent the reduction of the cycle characteristics that the pulverizing etc. by particle causes.In addition, be more than 1.0 through the lower limit that makes the P/N ratio, can guarantee high battery capacity.
(nonaqueous electrolyte)
As the nonaqueous electrolyte that uses in the non-aqueous secondary batteries of the present invention, can enumerate through dissolving inorganic lithium salt or organic lithium salt or the two electrolyte of modulating in following solvent.
As solvent; For example can use; Ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), gamma-butyrolacton, 1; 2-dimethoxy-ethane, oxolane, 2-methyltetrahydrofuran, methyl-sulfoxide, 1; 3-dioxolane, formamide, dimethyl formamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivative, sulfolane, 3-methyl-2-
oxazolidone, polypropylene carbonate ester derivant, tetrahydrofuran derivatives, ether, 1, more than 1 kinds or 2 kinds of non-proton organic solvent such as 3-propane sultone.
As inorganic lithium salt, can use LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiCF
3CO
2, LiAsF
6, LiSbF
6, LiB
10Cl
10, lower aliphatic carboxylic acid Li, LiAlCl
4, more than a kind or 2 kinds of LiCl, LiBr, LiI, chloroborane Li, tetraphenyl boric acid Li etc.
As organic lithium salt, can use LiCF
3SO
3, LiCF
3CO
2, Li
2C
2F
4(SO
3)
2, LiN (CF
3SO
2) 2, LiC (CF
3SO
2)
3, LiC
nF
2n+1SO
3(2≤n≤7), LiN (RfOSO
2)
2More than a kind or 2 kinds of (Rf is a fluoroalkyl here) etc.
The preferred use comprising at least a kind of linear carbonate that is selected from the group of being made up of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate and be selected from the solvent of at least a kind of cyclic carbonate in the group of being made up of ethylene carbonate and propylene carbonate is dissolved with LiPF
6Electrolyte.
The concentration of the lithium salts in the electrolyte is for example 0.2～3.0 mole/dm
3Be suitable, be preferably 0.5～1.5 mole/dm
3, 0.9～1.3 mole/dm more preferably
3
In addition; With the improvement of charge, make high-temperature storage characteristics, fail safe such as prevent to overcharge rises to purpose; In nonaqueous electrolytic solution, can also for example suitably contain; Acid anhydrides, sulphonic acid ester, dintrile, 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, vinylene carbonate, biphenyl, fluorobenzene, tert-butyl benzene, ring-type fluorocarbons acid esters (trifluoro propylene carbonate (TFPC), fluorine ethylidene carbonic ester (FEC) etc.) or chain fluorocarbons acid esters (derivatives that also comprises above-mentioned each compound) such as (trifluoro dimethyl carbonate (TFDMC), trifluoro diethyl carbonate (TFDEC), trifluoroethyl methyl carbonics (TFEMC) etc.).As stated, through limiting P/N ratio anodal and negative pole, can suppress by SiO
xThe expansion of the volume of/carbon complex, the pulverizing of shrinking the particle cause, and through TFPC being added in the nonaqueous electrolytic solution and at SiO
xThe particle surface of/carbon complex forms tunicle; Thereby even wait under the newborn situation about showing out making particle surface produce be full of cracks owing to discharging and recharging repeatedly; Also can be owing to the above-mentioned TFPC newborn face that is covered once more, thus the capacity deterioration that causes by charge and discharge cycles can be suppressed.In addition; TFPC compares with FEC; The resistance to oxidation reproducibility is high, therefore has to be difficult for causing the remaining decomposition reaction (gas generation etc.) except tunicle generates, and suppresses the exothermic reaction of accompanying with decomposition reaction and is difficult for causing the effect of the internal temperature rising of monocell (cell).
(dividing plate)
As the related dividing plate of non-aqueous secondary batteries of the present invention; Being preferably intensity fully and can keep the dividing plate of electrolyte in a large number, can used thickness be that 5～50 μ m and aperture opening ratio are micro-porous film 30～70%, polyethylene (PE), polypropylene polyolefin systems such as (PP).The micro-porous film that constitutes dividing plate can be for for example, only uses the micro-porous film of PE, only uses the micro-porous film of PP, can comprise ethylene-propylene copolymer, in addition, can be the laminated body of the micro-porous film of the micro-porous film of PE system and PP system.
In addition; The dividing plate that battery of the present invention is related can use by being that resin below 140 ℃ is that resin or heat resisting temperature more than 150 ℃ is the dividing plate of the lamination-type that constitutes as the porous layer (B) of main body of the inorganic filler more than 150 ℃ as the porous layer (A) of main body, with comprising fusing point with fusing point.Here; So-called " fusing point " is meant the regulation according to the K of Japanese Industrial Standards (JIS) 7121, uses differential scanning calorimetry (DSC) (DSC) to measure the fusion temperature that obtains; So-called " heat resisting temperature is more than 150 ℃ " is meant at least not observe softening grade for distortion at 150 ℃.
The related porous layer (A) of the dividing plate of above-mentioned lamination-type is mainly used in guarantees to close (shut down) function; Non-aqueous secondary batteries reaches as the fusing point of resin of the composition of the main body that becomes porous layer (A) when above; The resin fusion of porous layer (A) and stop up the hole of dividing plate produces closing of the carrying out that suppress electrochemical reaction.
Fusing point as the main body that becomes porous layer (A) is the resin below 140 ℃, can enumerate for example PE, as its form, can enumerate micro-porous film that uses in the lithium rechargeable battery or the form that on base materials such as nonwoven fabrics, is coated with the particle of PE.Here, in whole constituents of porous layer (A), the fusing point that becomes main body is that the volume of the resin below 140 ℃ is more than the 50 volume %, more preferably more than the 70 volume %.Form at the micro-porous film by above-mentioned PE under the situation of porous layer (A), making fusing point is that the volume of the resin below 140 ℃ is 100 volume %.
The porous layer (B) that the dividing plate of above-mentioned lamination-type is related is even possess the direct function that contacts the short circuit that causes that when the internal temperature of non-aqueous secondary batteries rises, also can prevent by anodal and negative pole, is that resin or heat resisting temperature more than 150 ℃ is that its function is guaranteed in inorganic filler more than 150 ℃ through fusing point.That is, be under the situation of high temperature at battery, even porous layer (A) shrinks, also can prevent the short circuit that the direct contact of generable both positive and negative polarity causes under the situation of dividing plate thermal contraction through the porous layer (B) that is difficult to shrink.In addition, owing to the skeleton of this stable on heating porous layer (B) as dividing plate works, therefore can also suppress the thermal contraction of porous layer (A), i.e. the whole thermal contraction itself of dividing plate.
Be that resin more than 150 ℃ forms under the situation of porous layer (B) as main body with fusing point; For example can enumerate, make by fusing point be micro-porous film (battery of for example above-mentioned PP system is used micro-porous film) that the resin more than 150 ℃ the forms form that is stacked on porous layer (A), to make fusing point be that resin-coated more than 150 ℃ goes up and the form of the coating lamination-type of lamination at porous layer (A).
As fusing point is the resin more than 150 ℃; For example can enumerate various cross-linked polymer particulates such as crosslinked polymethylmethacrylaparticles, crosslinked polystyrene, cross-linked divinylbenzene, styrene diethylene benzene copoly mer cross-linking agent, polyimides, melmac, phenol resin, benzoguanamine-formaldehyde condensation products; Thermal endurance high molecular particles such as PP, polysulfones, polyether sulfone, polyphenylene sulfide, polytetrafluoroethylene, polyacrylonitrile, aromatic polyamides, polyacetals.
Fusing point is that the particle diameter of the resin more than 150 ℃ is with average grain diameter D
50Meter for example is preferably more than the 0.01 μ m, more preferably more than the 0.1 μ m, in addition, is preferably below the 10 μ m, more preferably below the 2 μ m.
Because above-mentioned fusing point is that the amount of the resin more than 150 ℃ is involved as main body in porous layer (B); Therefore in the cumulative volume of the constituent of porous layer (B), be more than the 50 volume %; Be preferably more than the 70 volume %, more preferably more than the 80 volume %, further be preferably more than the 90 volume %.
Be that inorganic filler more than 150 ℃ forms under the situation of porous layer (B) as main body with heat resisting temperature; For example can enumerate; The dispersion liquid that will comprise heat resisting temperature and be inorganic filler more than 150 ℃ etc. is coated on the porous layer (A), and is dry and form the form of the coating lamination-type of porous layer (B).
The related inorganic filler of porous layer (B); So long as heat resisting temperature is more than 150 ℃, is stable with respect to the nonaqueous electrolytic solution that battery had, and gets final product in the inorganic filler that the operating voltage range of battery is difficult for the electrochemical stability of oxidized reduction; But from aspects such as dispersions; Be preferably particulate, in addition, be preferably aluminium oxide, silicon dioxide, boehmite.Therefore aluminium oxide, silicon dioxide, boehmite can control the porosity of porous layer (B) with particle diameter, shape adjustments to desired numerical value etc. easily accurately because oxidative resistance is high.In addition, be the inorganic filler more than 150 ℃ for heat resisting temperature, can for example above-mentioned illustrative inorganic filler be used a kind separately, also can be with also using more than 2 kinds.Perhaps, also can be the resin more than 150 ℃ with above-mentioned fusing point and use.
About the related heat resisting temperature of porous layer (B) is the shape of the inorganic filler more than 150 ℃, and not special restriction can be used roughly spherical (comprising spherical shape), roughly ellipsoid shaped (comprising ellipsoid shaped), different shape such as tabular.
In addition, if the related heat resisting temperature of porous layer (B) is the average grain diameter D of the inorganic filler more than 150 ℃
50(the average grain diameter of plate-like fillers and other shape filler.Below identical.) too small, then the permeability of ion reduces, and therefore is preferably more than the 0.3 μ m, more preferably more than the 0.5 μ m.In addition, excessive if heat resisting temperature is inorganic filler more than 150 ℃, then electrical characteristic is easy to deterioration, so its average grain diameter D
50Be preferably below the 5 μ m, more preferably below the 2 μ m.
Because the heat resisting temperature in the porous layer (B) is that the inorganic filler more than 150 ℃ is involved as main body in porous layer (B); Therefore the amount in porous layer (B) (with fusing point be under the situation of resin and usefulness more than 150 ℃, be meant the total amount of resin and inorganic filler.) in the cumulative volume of the constituent of porous layer (B), be more than the 50 volume %, be preferably more than the 70 volume %, more preferably more than the 80 volume %, further be preferably more than the 90 volume %.Through making the inorganic filler in the porous layer (B) is high-load as above-mentioned; Even thereby when non-aqueous secondary batteries is high temperature; Also can suppress the whole thermal contraction of dividing plate well, can further suppress well by the direct generation that contacts the short circuit that causes anodal and negative pole.
In the porous layer (B), in order to be that resin or heat resisting temperature more than 150 ℃ is that inorganic filler more than 150 ℃ is bonded to each other with fusing point, or integrated etc. for porous layer (B) and porous layer (A), preferably contain organic bond.As organic bond; Can enumerate ethylene-acrylic acid copolymer, fluorine such as vinyl-vinyl acetate copolymer (EVA, the construction unit that derives from vinyl acetate are 20～35 moles of %), ethylene-ethyl acrylate copolymer and be rubber, butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), polyvinyl alcohol (PVA), polyvinyl butyral resin (PVB), polyvinylpyrrolidone (PVP), cross-linked acrylic acid is resin, polyurethane, epoxy resin etc., the preferred especially stable on heating adhesive with heat resisting temperature more than 150 ℃ that uses.For organic bond, can above-mentioned illustrative organic bond be used a kind separately, also can be with also using more than 2 kinds.
In the above-mentioned illustrative organic bond, being preferably EVA, ethylene-acrylic acid copolymer, fluorine is the high adhesives of flexibility such as rubber, SBR.As the concrete example of the high organic bond of such flexibility, the SBR " BM-400B " of the SBR " TRD-2001 " of fluorubber " daiel latex series ", the JSR society of EEA, the Daikin Industries society of ethylene-acrylic acid copolymer " evaflex-EEA series ", the Japan Unicar society of EVA, the Polychemical society of Mitsui Du Pont of EVA " evaflex series ", the Japan Unicar society of Polychemical society of Mitsui Du Pont, Japanese Zeon society etc. is arranged.
Above-mentioned organic bond is being used under the situation of porous layer (B), if with after the porous layer (B) stated form dissolving in the solvent of composition of usefulness or the form of the emulsion of disperseing to form is used.
The dividing plate of above-mentioned coating lamination-type can be made as follows: for example; The porous layer (B) that will contain heat resisting temperature and be inorganic filler more than 150 ℃ etc. forms the surface that is coated on the micro-porous film that is used to constitute porous layer (A) with composition fluid compositions such as (etc.) slurries; At the temperature drying of regulation, form porous layer (B).
Composition is used in formation about porous layer (B), except heat resisting temperature is the inorganic filler more than 150 ℃, contains organic bond etc. as required, makes them be dispersed in solvent and (comprises decentralized medium.Below identical.) in form.About organic bond, also can be dissolved in the solvent.Porous layer (B) forms with the solvent that uses in the composition, as long as can disperse inorganic filler etc. equably, in addition, can dissolve equably or disperse organic bond to get final product, suitable use for example, aromatic hydrocarbons such as toluene; Furans such as oxolane; Ketone such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Etc. general organic solvent.In addition, in these solvents, be purpose with the control interfacial tension, can suitably add various propylene oxides such as alcohol (ethylene glycol, propane diols etc.) or monomethyl acetic acid esters is glycol ethers etc.In addition, be under the water miscible situation at organic bond, inferior in situation about using as emulsion, can be with water as solvent, can also suitably add alcohols (methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol etc.) and control interfacial tension this moment.
Porous layer (B) forms with in the composition, makes preferably that to comprise heat resisting temperature be that the solid component content of inorganic filler and organic bond etc. more than 150 ℃ is for example 10～80 quality %.
In the dividing plate of above-mentioned lamination-type, it is 1 layer respectively respectively that porous layer (A) and porous layer (B) do not need, and in dividing plate, can have multilayer.For example, can become the formation that disposes porous layer (A) on the two sides of porous layer (B), also can become the formation that disposes porous layer (B) on the two sides of porous layer (A).Yet; Through increasing the number of plies; Might increase the thickness of dividing plate and cause the internal resistance increase of battery, energy density to reduce, it is not preferred therefore excessively increasing the number of plies, and the total number of plies of porous layer in the dividing plate of above-mentioned lamination-type (A) and porous layer (B) is preferably below 5 layers.
The thickness of the related dividing plate of non-aqueous secondary batteries of the present invention (dividing plate that is made up of the micro-porous film of polyolefin system, the dividing plate of above-mentioned lamination-type) is 10～30 μ m more preferably.
In addition; In the dividing plate of above-mentioned lamination-type, for the thickness ［ dividing plate has under the situation of a plurality of porous layers (B), is its gross thickness ］ of porous layer (B); From more effectively bringing into play the viewpoint of above-mentioned each effect that brings by porous layer (B), be preferably more than the 3 μ m.Yet,, might cause the reduction etc. of the energy density of battery, so the thickness of porous layer (B) is preferably below the 8 μ m if porous layer (B) is blocked up.
In addition, in the dividing plate of above-mentioned lamination-type, ［ dividing plate has under the situation of a plurality of porous layers (A), is its gross thickness for the thickness of porous layer (A).Below identical., from more effectively bringing into play viewpoint, be preferably more than the 6 μ m, more preferably more than the 10 μ m by the above-mentioned effect that use brought (particularly closing function) of porous layer (A).Yet, if porous layer (A) is blocked up, might cause the reduction of the energy density of battery, in addition, might want the power of thermal contraction to increase by porous layer (A), the effect that suppresses the whole thermal contraction of dividing plate reduces.Therefore, the thickness of porous layer (A) is preferably below the 25 μ m, more preferably below the 18 μ m, further is preferably below the 16 μ m.
As the whole porosity of dividing plate, in order to ensure guarantor's liquid measure of electrolyte and make ion permeability good, preferably be more than 30% under dry status.On the other hand, guarantee and the viewpoint that prevents of internal short-circuit that from diaphragm strength the porosity of dividing plate preferably is below 70% under dry status.The porosity of dividing plate: P (%) can be used following formula (1) to obtain the summation of each component i, thereby calculated by the thickness of dividing plate, the quality of unit are, the density of constituent.
P＝100－(∑a
i/ρ
i)×(m/t) (1)
Here, in the above-mentioned formula (1), a
i: the ratio of the component i of representing with quality %, ρ
i: the density (g/cm of component i
3), m: the quality (g/cm of the per unit area of dividing plate
2), t: the thickness of dividing plate (cm).
In addition, under the situation of the dividing plate of above-mentioned lamination-type, can also m be made as the quality (g/cm of the per unit area of porous layer (A) through in above-mentioned formula (1)
2), the thickness (cm) with t is made as porous layer (A) uses above-mentioned formula (1) to obtain the porosity of porous layer (A): P (%).The porosity of the porous layer of obtaining through this method (A) is preferably 30～70%.
In addition, under the situation of the dividing plate of above-mentioned lamination-type, can also m be made as the quality (g/cm of the per unit area of porous layer (B) through in above-mentioned formula (1)
2), the thickness (cm) with t is made as porous layer (B) uses above-mentioned formula (1) formula to obtain the porosity of porous layer (B): P (%).The porosity of the porous layer of obtaining through this method (B) is preferably 20～60%.
As aforementioned barriers, be preferably the high dividing plate of mechanical strength, preference is more than the 3N as piercing through intensity.The negative electrode active material that uses in the non-aqueous secondary batteries of the present invention as stated because the expansion of the volume when discharging and recharging, shrink big, therefore in the present invention through with the P/N proportional limit built in 1.0～3.6 suppress volume expansion, contraction, improve cycle characteristics.Yet,, also bring mechanical damage for the dividing plate of being faced owing to the flexible of negative pole integral body through repeating charge and discharge cycles repeatedly.If the intensity that pierces through of dividing plate is more than the 3N, then can guarantee excellent mechanical intensity, relax the suffered mechanical damage of dividing plate.
As piercing through intensity is the dividing plate more than the 3N; Can enumerate the dividing plate of above-mentioned lamination-type, be that resin below 140 ℃ has as porous layer (A) superimposed layer of main body that to comprise heat resisting temperature be that inorganic filler more than 150 ℃ is particularly suitable as the dividing plate of the porous layer (B) of main body with fusing point.Think that this is because the mechanical strength of above-mentioned inorganic filler is high, therefore can compensate the mechanical strength of porous layer (A), improves the whole mechanical strength of dividing plate.
The above-mentioned intensity that pierces through can adopt following method to measure.Not having fold, not have crooked mode stationary barrier, to be the spherical metal needle of the semicircle of 1.0mm fall to measuring sample with the speed of 120mm/min the diameter that makes front end on the plate in the hole that has 2 inches diameter, and the power in the time of will be to the dividing plate perforate is measured 5 times.Then,, obtain mean value, it is made as the intensity that pierces through of dividing plate for remaining 3 times the mensuration of removing maximum and minimum value in the above-mentioned 5 times measured value.
Can be between positive pole and negative pole, the to have dividing plate overlapping laminate electrode body of above-mentioned positive pole, above-mentioned negative pole and above-mentioned dividing plate, the form that further is wound into spiral helicine rolled electrode body are used for non-aqueous secondary batteries of the present invention.
In above-mentioned laminate electrode body, the rolled electrode body; State in the use under the situation of dividing plate of lamination-type; Particularly use is being that resin below 140 ℃ has as porous layer (A) superimposed layer of main body that to comprise heat resisting temperature be that porous layer (B) preferably is configured with relative with positive pole at least mode under the situation of inorganic filler as the dividing plate of the porous layer (B) of main body more than 150 ℃ with fusing point.In this case; Comprise heat resisting temperature and be inorganic filler more than 150 ℃ as the more excellent porous layer (B) of main body, oxidative resistance through relative with positive pole; The oxidation of the dividing plate that can suppress more well to cause by positive pole, preservation characteristics, charge in the time of therefore can also improving the high temperature of battery.In addition, in nonaqueous electrolytic solutions such as vinylene carbonate, cyclohexyl benzene, add under the situation of additive, also at side of the positive electrode the pore of dividing plate is stopped up sometimes, battery behavior is reduced significantly.Therefore through the porous layer (B) than porous is faced with positive pole, can also expect to suppress the effect of the obstruction of pore.
On the other hand; Surface a side of above-mentioned lamination-type dividing plate is under the situation of porous layer (A); Porous layer (A) is preferably relative with negative pole, thus, and for example; Be absorbed into the mixture layer of electrode in the time of can suppressing to close by the thermoplastic resin of porous layer (A) fusion, be used for the obturation of the hole of dividing plate expeditiously.
(form of battery)
As the form of non-aqueous secondary batteries of the present invention, not special restriction.Can be for for example, coin shape, buckle any of the large-scale form used in shape, sheet shape, lamination shape, cylindrical shape, pancake, square, the electric automobile etc. etc.In addition; As stated; If use above-mentioned negative electrode active material, then using the outer tinning of thickness is little for width square (square tubular), pancake outer tinning, laminated film exterior body to wait under the situation of the battery that constitutes, the problem that battery is heaved is easy to generation especially; But in the battery of the present invention; Can suppress the generation that such battery is heaved well, therefore under the situation of the rectangular cell of processing exterior body (outer tinning), flat-shaped battery, show its effect especially significantly with above-mentioned that kind.
In addition; When in non-aqueous secondary batteries, importing positive pole, negative pole and dividing plate; According to the form of battery, can also as with a plurality of positive poles and a plurality of negative pole across dividing plate and the laminate electrode body of lamination, with positive pole and negative pole across dividing plate and lamination further is wound into spiral helicine rolled electrode body uses.In addition, if SiOx is used as negative electrode active material, then particularly under the situation of processing the rolled electrode body; The problem that is caused by distortion such as the change in volume of negative pole is easy to take place; But used the battery of negative pole of the present invention, that is, and in the battery of the present invention; Can suppress the distortion such as change in volume of such negative pole well; Therefore have the rolled electrode body processing (particularly, rectangular cell, used pancake outside the employed cross section vertical such as the flat-shaped battery of tinning, laminated film exterior body etc. with wireline reel be the rolled electrode body of flat) the situation of battery under, show its effect especially significantly.
Non-aqueous secondary batteries of the present invention be that the various battery behaviors of representative are good with the charge, therefore can bring into play these characteristics and be preferred for being suitable in the various uses of known all the time non-aqueous secondary batteries that power supply with small-sized and multi-functional portable equipment is representative.
Embodiment
Below, describe the present invention in detail based on embodiment.Yet following embodiment does not limit the present invention.
(embodiment 1)
The making of＜positive pole＞
Will be as the LiCoO of positive active material
2: 70 mass parts and LiMn
0.2Ni
0.6Co
0.2O
2: 30 mass parts, as the Delanium of conductive auxiliary agent: 1 mass parts and Ketjen black: 1 mass parts and in the NMP as solvent, mix as the PVDF:10 mass parts of adhesive modulates the thickener that contains anode mixture.The above-mentioned thickener that contains anode mixture is regulated the two sides that thickness ground is coated on the collector body that the aluminium foil by thickness 15 μ m constitutes intermittence; After the drying; Roll processing; Adjust the thickness of anode mixture layer so that gross thickness is the mode of 130 μ m, cut off and make positive pole so that width is the mode of 54.5mm.Exposed division welding fin at this anodal aluminium foil forms leading part then.
The making of＜negative pole＞
With average grain diameter D
50Be the SiO of 5 μ m
x/ carbon complex and average grain diameter D
50The graphite matter carbon that is 16 μ m is with the composite mixture of the mass ratio of 5:95: 98 mass parts, be adjusted into the CMC aqueous solution of concentration of 1 quality % of the scope of 1500～5000mPas as the viscosity of adhesive: 1.0 mass parts, SBR:1.0 mass parts, be 2.0 * 10 as the ratio conductivity of solvent
5The above ion exchange water of Ω/cm mixes, and modulates the thickener that contains cathode agent of water system.
Here, SiO
xThe amount of coating of the carbon the in/carbon complex is 20 quality %, the I of the Raman spectrum when measuring optical maser wavelength 532nm
510/ I
1343Strength ratio is 0.10, has used the Alpha-ray SiO of CuK
xSi (111) the diffraction maximum half width of X-ray diffraction when measuring be 1.0 °.
The above-mentioned thickener that contains cathode agent is regulated the two sides that thickness ground intermittently is coated on the collector body of the thickness 8 μ m that are made up of Copper Foil; After the drying; Roll processing; Adjust the thickness of anode mixture layer so that gross thickness is the mode of 110 μ m, cut off and make negative pole so that width is the mode of 55.5mm.Exposed division welding fin at the Copper Foil of this negative pole forms leading part then.
The making of＜dividing plate＞
At average grain diameter D
50Be to add ion exchange water 5kg and dispersant (water system polycarboxylic acids ammonium salt, solid component concentration 40 quality %) 0.5kg among the boehmite 5kg of 1 μ m, the ball mill that employing internal volume 20L, rotating speed are 40 times/minute carried out pulverization process 10 hours, modulated dispersion liquid.120 ℃ of vacuumizes, (SEM) observes with scanning electron microscope with the dispersion liquid after handling, and the result is that being shaped as of boehmite is roughly tabular.
In above-mentioned dispersion liquid 500g, add xanthan gum 0.5g as thickener, as resin-bonding agent dispersion (the modified polypropene acid butyl ester of adhesive; Solid component content 45 quality %) 17g; Adopt mixer to stir 3 hours; Modulate uniform slurry ［ porous layer (B) forms and uses slurry, solid constituent ratio 50 quality % ］.
Next, lithium rechargeable battery is implemented Corona discharge Treatment (discharge capacity 40Wmin/m with the one side of the micro-porous dividing plate of PE system ［ porous layer (A): thickness 12 μ m, porosity 40%, average pore size 0.08 μ m, 135 ℃ of the fusing points of PE ］
2), on this treated side, use slurry through the applying porous matter layer of nick format coating machine (B) formation, carry out drying, forming thickness is the porous layer (B) of 4 μ m, obtains the dividing plate of lamination-type.The quality of the per unit area of the porous layer in this dividing plate (B) is 5.5g/m
2, the volume content of boehmite is 95 volume %, porosity is 45%.
The modulation of＜nonaqueous electrolytic solution＞
With EC, MEC, DEC and VC with the composite mixed solvent of volume ratio 2:3:1:0.2, with TFPC and TFDMC respectively with the mixed of 30 volume %, 30 volume % and 40 volume %, make LiPF as lithium salts
6With 1 mole/dm of concentration
3Dissolving modulates nonaqueous electrolytic solution.
The assembling of＜battery＞
The porous layer (B) that makes dividing plate carries out overlapping between above-mentioned such positive pole that obtains and negative pole simultaneously with the mode relative with positive pole, be wound into helical form and make the rolled electrode body.Push the rolled electrode body of gained and become flat, put into the outer tinning of aluminium alloy system of thickness 5mm, width 42mm, height 61mm, inject the nonaqueous electrolytic solution of modulation as stated.
Carry out the sealing of outer tinning after the injection of nonaqueous electrolytic solution, make the non-aqueous secondary batteries of structure shown in Figure 1A, the 1B and outward appearance shown in Figure 2.This battery possesses the cracking mouth that is used to reduce pressure under the situation that in the top of jar, presses liter.
Here Figure 1A, 1B and battery shown in Figure 2 are described; Figure 1A is a plane graph; Figure 1B is a sectional view, and shown in Figure 1B, positive pole 1 and negative pole 2 are after dividing plate 3 is wound into helical form; Pressurize with the mode that becomes flat and process the rolled electrode body 6 of flat, in the outer tinning 4 of the nonaqueous electrolytic solution side of being accommodated in tubular.But, among Figure 1B, for fear of complicated, the metal forming of employed collector body, electrolyte etc. during not shown making as anodal 1, negative pole 2.In addition, also not difference expression of each layer of dividing plate.
Outer tinning 4 is aluminium alloy system and the exterior body that constitutes battery, these outer tinning 4 double as positive terminals.And; The bottom of tinning outside 4 disposes the insulator 5 that is made up of polyethylene (PE) sheet, draws positive wire body 7 and the negative wire body 8 that is connected with an end separately of negative pole 2 with anodal 1 from the rolled electrode body 6 that comprises positive pole 1, negative pole 2 and the flat of dividing plate 3.In addition, sealing with being situated between on the cover plate 9 of the aluminium alloy system of the peristome of tinning 4 is equipped with the terminal 11 of stainless steel by the insulating sealer 10 of polypropylene (PP) system outside sealing, and being situated between on this terminal 11 is equipped with the lead plate 13 of stainless steel by insulator 12.
And cover plate 9 is inserted in the peristome of outer tinning 4, seals the peristome of outer tinning 4 through the junction surface of welding both, and inside battery is sealed.In addition, in the battery of Figure 1A, 1B, cover plate 9 is provided with nonaqueous electrolytic solution inlet 14, in this nonaqueous electrolytic solution inlet 14, is inserted with under the state of seal member, for example carries out welded seal through laser welding etc., guarantees the seal of battery.Therefore, in the battery of Figure 1A, 1B and Fig. 2, in fact nonaqueous electrolytic solution inlet 14 is nonaqueous electrolytic solution inlet and seal member, but in order to make explanation easily, as 14 expressions of nonaqueous electrolytic solution inlet.When in addition, cover plate 9 is provided with cracking mouthfuls 15 and rises as battery temperature gas inside is expelled to the mechanism of outside.
In the battery of this embodiment 1; Through positive wire body 7 directly is welded on the cover plate 9, outer tinning 4 and cover plate 9 are worked, as positive terminal through negative wire body 8 is welded on the lead plate 13; Jie makes negative wire body 8 and terminal 11 conductings by this lead plate 13; Thereby terminal 11 is worked, but according to the difference of material of outer tinning 4 etc. as negative terminal, also its positive and negative putting upside down sometimes.
Fig. 2 is the stereogram of the outward appearance that shows the battery shown in above-mentioned Figure 1A, the 1B, and this Fig. 2 is in order to show that above-mentioned battery is a rectangular cell and illustrated, roughly to show battery among this Fig. 2, and only diagram constitutes the certain components in the parts of battery.In addition, among Figure 1B, do not show the shade that for the central portion of rolled electrode body 6 and dividing plate 3, shows the cross section yet.
(embodiment 2～4)
Will be as the SiO of negative electrode active material
xThe carbon amount of coating of/carbon complex, the I of Raman spectrum
510/ I
1343Strength ratio and SiO
xSi (111) the diffraction maximum half width that kind as shown in table 1 of X-ray diffraction change, in addition, all likewise operate and make non-aqueous secondary batteries with embodiment 1.
(comparative example 1～4)
With SiO
xThe carbon amount of coating of/carbon complex, the I of Raman spectrum
510/ I
1343Strength ratio and SiO
xSi (111) the diffraction maximum half width as shown in table 1 that kind of X-ray diffraction when measuring change, in addition, all likewise operate and make non-aqueous secondary batteries with embodiment 1.
Non-aqueous secondary batteries about making in the foregoing description 1～4 and the comparative example 1～4 carries out following storage test (25 ℃ of storages and 45 ℃ of storages).Their result is shown in Table 2.
＜25 ℃ of storage tests＞
At 25 ℃, after the constant current of employing 1C (being equivalent to 1200mA) and the constant voltage of voltage 4.2V are carried out constant current-constant voltage charge (total charging time: 3 hours), carry out constant-current discharge (final discharging voltage: 2.7V), measure the discharge capacity (mAh) at initial stage with 1C.
After the discharge capacity at initial stage is measured, adopt the constant current of 0.5C (being equivalent to 600mA) and the constant voltage of voltage 4.2V to carry out constant current-constant voltage charge (total charging time: 1 hour) at 25 ℃ on each battery, in 25 ℃ thermostat, store 7 days.After the storage, carry out constant-current discharge (final discharging voltage: 2.7V) with 1C.
For the discharge capacity after confirming to store; At 25 ℃; After the constant current of employing 1C (being equivalent to 1200mA) and the constant voltage of voltage 4.2V are carried out constant current-constant voltage charge (total charging time: 3 hours), carry out constant-current discharge (final discharging voltage: 2.7V), measure the discharge capacity (mAh) after storing with 1C.Discharge capacity after storing is obtained as the presented higher holdup with respect to the ratio of the discharge capacity before storing.
＜45 ℃ of storage tests＞
Except the temperature conditions that will store with thermostat is made as 45 ℃, all likewise operate making an experiment with 25 ℃ of storage tests.
[table 1]
[table 2]
About making SiO as negative electrode active material
xCarbon content in the/carbon complex is 10～30 quality %, and makes above-mentioned SiO
xIn the Raman spectrum of/carbon complex, derive from the 510cm of Si
-1Peak intensity: I
510With the 1343cm that derives from C
-1Peak intensity: I
1343Strength ratio: I
510/ I
1343Be below 0.25, the half width at the X-ray diffraction peak of (111) face of the Si phase that core comprised is less than the non-aqueous secondary batteries of 3.0 ° embodiment 1～4, and the initial stage discharge capacity is big, in the storage of 25 ℃ and 45 ℃, has obtained excellent presented higher holdup.Particularly, the half width at the X-ray diffraction peak of (111) face of the Si phase that core comprised is the non-aqueous secondary batteries of the embodiment 1～3 more than 0.5 °, and the initial stage discharge capacity is high value.
On the other hand, SiO
xCarbon content in the/carbon complex is less than comparative example 1 and the strength ratio of 10 quality %: I
510/ I
1343The half width at the X-ray diffraction peak of (111) face of the comparative example 2 above 0.25, the Si phase that core comprised is in the comparative example 4 more than 3.0 °, and the presented higher holdup is not good in 45 ℃ storage.SiO
xCarbon content in the/carbon complex surpasses in the comparative example 3 of 30 quality %, and the initial stage discharge capacity is insufficient.
Therefore, can know SiO
xCarbon content in the/carbon complex is preferably 10～30 quality %.In addition, can know strength ratio: I
510/ I
1343Be preferably below 0.25.In addition, the half width at X-ray diffraction peak of (111) face that can know the Si phase that core comprises is preferably less than 3.0 °, more preferably more than 0.5 ° below 2.5 °.
The mode of the present invention beyond can also be in the above described manner in the scope that does not break away from its main idea implemented.Disclosed execution mode is an example among the application, is not limited to this.The record of appending claims has precedence over the record of above-mentioned specification and explains scope of the present invention, with the impartial scope of claims in whole changes be included in claims.
The industry utilizability
Non-aqueous secondary batteries of the present invention is a high power capacity; And have excellent battery behavior, therefore can bring into play these characteristics and be preferred for being suitable in the various uses of known all the time non-aqueous secondary batteries that power supply with small-sized and multi-functional portable equipment is representative.
The explanation of symbol
1 positive pole
2 negative poles
3 dividing plates
4 outer tinnings
5 insulators
6 rolled electrode bodies
7 utmost points lead-in wire body
8 negative wire bodies
9 seal and use cover plate
10 insulating sealers
11 terminals
12 insulators
13 lead plates
14 nonaqueous electrolytic solution inlets
15 cracking mouths.
Claims (8)
1. a non-aqueous secondary batteries is characterized in that, is the non-aqueous secondary batteries that comprises positive pole, negative pole, nonaqueous electrolyte and dividing plate,
Said negative pole contains negative electrode active material, and said negative electrode active material contains: in constituting element, contain complex and graphite matter material with carbon element that the coating of surface formation carbon of the core of Si and O forms,
Carbon content in the said complex is 10～30 quality %,
When measuring the Raman spectrum of said complex, derive from the 510cm of Si with optical maser wavelength 532nm
-1Peak intensity I
510With the 1343cm that derives from carbon
-1Peak intensity I
1343Strength ratio I
510/ I
1343Be below 0.25,
When having used the Alpha-ray X-ray diffraction method of CuK to measure the crystallite size of the Si phase that said core comprised, the half width of (111) diffraction maximum of Si is less than 3.0 °.
2. non-aqueous secondary batteries according to claim 1, the said half width of (111) diffraction maximum of Si is below 2.5 °.
3. non-aqueous secondary batteries according to claim 1, the said half width of (111) diffraction maximum of Si is more than 0.5 °.
4. non-aqueous secondary batteries according to claim 1, the said coating of said complex are that the thermal decomposition when hydrocarbon system gas is heated in gas phase forms.
5. non-aqueous secondary batteries according to claim 1, the material that contains Si and O in the said formation element is to form general formula SiO
xExpression,
In said composition general formula, x is 0.5≤x≤1.5.
6. non-aqueous secondary batteries according to claim 1, the content of the said complex in the said negative electrode active material is more than the 0.01 quality % below the 20 quality % with respect to said negative electrode active material integral body.
7. non-aqueous secondary batteries according to claim 1, the average grain diameter of said complex are 0.5～20 μ m.
8. non-aqueous secondary batteries according to claim 1, when the quality with the positive active material of said positive pole be made as P, when the quality of the said negative electrode active material of said negative pole is made as N, P/N is 1.0～3.6.
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Also Published As
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| JP5756063B2 (en) | 2015-07-29 |
| KR101741666B1 (en) | 2017-05-30 |
| US8481212B2 (en) | 2013-07-09 |
| CN103560225B (en) | 2016-08-17 |
| KR101181944B1 (en) | 2012-09-11 |
| JPWO2012036127A1 (en) | 2014-02-03 |
| KR20130040767A (en) | 2013-04-24 |
| EP2618406A4 (en) | 2014-03-05 |
| JP5042400B2 (en) | 2012-10-03 |
| CN103560225A (en) | 2014-02-05 |
| US20120288742A1 (en) | 2012-11-15 |
| CN102792493B (en) | 2015-03-11 |
| KR20120080256A (en) | 2012-07-16 |
| US20130273439A1 (en) | 2013-10-17 |
| WO2012036127A1 (en) | 2012-03-22 |
| EP2618406A1 (en) | 2013-07-24 |
| US8859147B2 (en) | 2014-10-14 |
| JP2012227154A (en) | 2012-11-15 |
| EP2618406B1 (en) | 2016-06-22 |
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